CN113800569B - Recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag - Google Patents
Recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag Download PDFInfo
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- CN113800569B CN113800569B CN202010527152.2A CN202010527152A CN113800569B CN 113800569 B CN113800569 B CN 113800569B CN 202010527152 A CN202010527152 A CN 202010527152A CN 113800569 B CN113800569 B CN 113800569B
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- molybdenum
- copper
- tungsten
- acid
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 61
- 239000011733 molybdenum Substances 0.000 title claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 239000010949 copper Substances 0.000 title claims abstract description 54
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 44
- 239000010937 tungsten Substances 0.000 title claims abstract description 44
- 239000002893 slag Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 23
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 23
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 23
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000011084 recovery Methods 0.000 title claims description 18
- 239000000243 solution Substances 0.000 claims abstract description 42
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 9
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 7
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000003916 acid precipitation Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- APCLRHPWFCQIMG-UHFFFAOYSA-N 4-(5,6-dimethoxy-1-benzothiophen-2-yl)-4-oxobutanoic acid Chemical compound C1=C(OC)C(OC)=CC2=C1SC(C(=O)CCC(O)=O)=C2 APCLRHPWFCQIMG-UHFFFAOYSA-N 0.000 description 3
- 229940125791 MSA-2 Drugs 0.000 description 3
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 3
- 101710162106 Merozoite surface antigen 2 Proteins 0.000 description 3
- -1 electronics Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a recycling method for preparing ammonium molybdate, tungsten, copper and sulfur by removing molybdenum slag, which comprises the following main steps: the molybdenum-removed slag is subjected to high-temperature high-pressure oxidation conversion under the condition of ammonia medium, so that the leaching rate is improved; acid-precipitating the leaching solution to obtain a mixture containing molybdic acid and tungstic acid, and dissolving the mixture in ammonia water to obtain a crude ammonium molybdate solution; removing tungsten from the ammonium molybdate solution by two steps of tungsten removal through adsorption and ion exchange, and recovering a corresponding crude tungstic acid product; removing small amounts of divalent metal ions present in the solution by ammonium sulfide; preparing an ammonium heptamolybdate product by vacuum crystallization; the separated copper-containing solution is used for recovering metallic copper by an electrodeposition method, and the electrodeposited mother solution is used for recovering ammonium sulfate by a triple effect evaporator. The invention has the advantages that the ammonium heptamolybdate product meeting the national standard is recovered from the molybdenum removal slag, and simultaneously, all the effective components of the molybdenum removal slag are recovered, thereby realizing the secondary recycling of all the components of the molybdenum removal slag.
Description
[ field of technology ]
The invention relates to the technical field of metal wet smelting and resource regeneration, in particular to a recovery method for preparing ammonium molybdate and tungsten, copper and sulfur by removing molybdenum slag.
[ background Art ]
Molybdenum and tungsten belong to VIB group elements in periodic table, are silver white high-melting point metals, are inactive at normal temperature, and do not act with most nonmetallic elements. Molybdenum and tungsten have a wide range of uses in modern industrial fields such as steel, electronics, petroleum, chemical, medicine, etc. Molybdenum and tungsten also play different roles in some industrial fields, for example tungsten is widely used for manufacturing various filaments and heating elements of electric furnaces, and molybdenum is an indispensable component in catalysts. With the continuous development of industrial scale, the production of molybdenum and tungsten products from mineral resources of molybdenum and tungsten is increasingly limited by the shortage of reserves in nature, and the secondary recycling of molybdenum and tungsten is an important way for solving the shortage of mineral resources. Today, technological studies on secondary recycling of various molybdenum and tungsten are active.
Molybdenum and tungsten are highly similar in physical and chemical properties as they belong to group VIB. In mineral reserves in nature, the two are often associated with each other. This results in the production of tungsten and molybdenum-containing waste residues, respectively, during the industrial production of molybdenum and tungsten articles. The secondary recycling of the waste residues has good resource and environmental protection significance.
Copper is one of ten nonferrous metals, has good physical and chemical properties, and has wide application in the industrial field. Although the natural reserves of copper are relatively richer than molybdenum and tungsten, the copper reserves of China account for only 4.12 percent of the global copper reserves due to the larger industrial demand, and copper resources are relatively scarce. The secondary recycling of copper plays an important role in national economy construction.
Ammonium paratungstate is an important product in tungsten product industry applications and is a raw material for manufacturing tungsten trioxide and tungsten metal powder. Because tungsten products have very strict limits on the content of impurities in application, the removal requirement on the impurities is very high in the production process of ammonium paratungstate. The impurities such as phosphorus, arsenic, silicon and the like are relatively easy to remove in the production, and the removal of molybdenum is difficult and complex. The conventional methods for molybdenum removal of ammonium tungstate solution in the current ammonium paratungstate production include a selective precipitation method, an extraction method and an ion exchange method. The selective precipitation method is widely applied to the production of ammonium paratungstate due to clear principle, good effect and easy operation. The principle is that under the proper temperature and pH condition, the water is led toAdding ammonium sulfide into ammonium tungstate solution containing molybdate to carry out vulcanization reaction, and selectively adding MoO 4 2- Sulfur to MoS 4 2- Then adding CuSO into the vulcanized material 4 The solution is reacted to form insoluble CuMoS 4 Precipitating, filtering and separating to obtain purified ammonium tungstate solution and a filter cake, namely molybdenum removal slag.
The molybdenum-removing slag contains molybdenum, copper and sulfur as main components and a certain amount of tungsten, wherein different elements are recovered to generate different economic values, and the comprehensive recovery of the elements is the final target. Chinese patents CN201210375776.2, CN201811366398.5, CN201810848354.X and CN201710476682.7 disclose methods for molybdenum and copper recovery from molybdenum slag, the resulting products are all metal molybdates, mainly sodium molybdate and calcium molybdate, and copper products of different forms. Chinese patent CN201811308570.1 discloses a method for preparing ammonium phosphotungstate from molybdenum slag. Chinese patent CN201810845345.5 discloses a method for preparing iron molybdate from molybdenum-removed slag. Chinese patent CN201010555831.7 discloses a method for recovering tungsten from molybdenum-removed slag. In the above methods, only a part of the components of the molybdenum-removed slag is recovered, and other components may become useless waste. Chinese patent CN201811366395.1 and CN201910982680.4 disclose methods for recovering molybdenum, copper, tungsten and sulfur from molybdenum-removed slag, respectively, the former adopts wet leaching to remove molybdenum slag, the leaching degree is not high enough, the recovery rate of molybdenum is limited, and the latter carries out high-temperature roasting to remove molybdenum slag to produce sulfide gas pollution. Chinese patent CN201310429671.5 and CN201410529610.0 disclose a method for preparing crude ammonium molybdate from molybdenum-removed slag, in which the former directly leaches molybdenum-removed slag with low leaching rate, and the latter is subjected to resistance furnace roasting, which has environmental pollution problem.
The method for producing ammonium molybdate by using molybdenum ore as a resource has the widely used technical route at present that molybdenum concentrate is roasted at high temperature to prepare molybdenum calcine and sulfuric acid is co-produced, and the prepared molybdenum calcine is subjected to ammonia leaching to realize higher molybdenum leaching rate. In addition, there is a technical route for directly leaching molybdenite raw material, in which a mixture of an oxidant, an alkaline leaching agent and the like is utilized to convert molybdenum disulfide of molybdenite into molybdate anions under high temperature and high pressure conditions, and simultaneously, negative divalent sulfur is converted into hexavalent sulfur to form sulfate anions. Chinese patent CN201610906901.6 discloses a method for co-producing ammonium molybdate and ammonium sulfate by treating molybdenite with oxygen pressure water leaching method.
The basic composition of the molybdenum-removed slag can be expressed as CuMoS 4 Wherein the valence state of sulfur is minus 2. The alkaline leaching, acid leaching and ammonia leaching are carried out under normal pressure, the total leaching rate is not high, and the technical route is easy to cause the waste of molybdenum and tungsten. The sulfur oxide is converted into molybdenum oxide and copper oxide by adopting a roasting method, and sulfur oxide gas is generated in the roasting process, so that pollution is easy to cause. The Chinese patent CN201810848354.X discloses a method for preparing sodium molybdate products by treating molybdenum slag under high temperature and high pressure conditions by using sodium hydroxide solution as a medium and industrial oxygen as an oxidant.
[ invention ]
The invention aims to provide a recycling method for preparing ammonium molybdate, tungsten, copper and sulfur from molybdenum-removed slag, so as to fully recycle various secondary recycling components in the molybdenum-removed slag generated in the production of ammonium paratungstate.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the application discloses a recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by removing molybdenum slag, which comprises the following steps:
a) High pressure oxygen leaching: crushing, grinding and sieving molybdenum-removing slag, adding 200-300 mesh undersize powder into an autoclave, adding ammonia water at the same time, then introducing oxygen into the autoclave through a pipeline, controlling the oxygen partial pressure to be 2.3-2.7 MPa, heating the autoclave to be at 90-110 ℃, reacting for 8-10 hours under stirring, taking out the solution after the autoclave is cooled to 40 ℃, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals and filter residues;
b) Acid precipitation: regulating the pH value of the mixed solution obtained in the step a) to 3.5-4.5 by using 10% inorganic acid, and carrying out solid-liquid separation to obtain a mixed filter cake of molybdic acid and tungstic acid and a filtrate containing copper sulfate respectively;
c) Ammonia dissolution: dissolving the mixed filter cake obtained in the step b) by ammonia water, regulating the pH value to 8.0-8.9, completely dissolving the precipitate, and filtering to remove a small amount of undissolved impurities to obtain a mixed solution containing molybdate and tungstate;
d) Adsorbing and removing tungsten: regulating the pH value of the mixed solution obtained in the step c) to 9.0-10.0 under the condition of stirring, and dropwise adding 2mol/L FeCl 3 Dissolving, adding 10% HNO 3 Regulating the pH value to 6.5-7.0, stirring for 4 hours, and filtering to obtain filtrate, wherein a filter cake is crude tungstic acid;
e) Purifying: maintaining the filtrate obtained in the step d) at 85-90 ℃ and under the condition that the pH value is 8.0-10.0, adding a proper amount of sulfide to precipitate and purify divalent metal in the solution for 3-5 hours, filtering the liquid to obtain filtrate, and discarding a filter cake;
f) Ion exchange: regulating the pH value of the filtrate obtained in the step e) to 7.5-8.5 by using 10% inorganic acid, and then passing the filtrate through an ion exchange column, adsorbing tungstate radicals on the ion exchange column, and flowing out molybdate radicals to obtain a post-exchange liquid;
g) And (3) vacuum crystallization: regulating the pH value of the mixed solution obtained in the step f) to 6.0-7.0, maintaining the temperature of a crystallization kettle at 70-80 ℃, and crystallizing under vacuum condition to obtain ammonium heptamolybdate;
h) Desorbing, precipitating and filtering: desorbing the ion exchange column adsorbing the tungstate radical in the step f) by ammonia water or sodium hydroxide solution to obtain ammonium tungstate or sodium tungstate solution, regulating the pH value of the ammonium tungstate or sodium tungstate solution to 3.0-4.0 by inorganic acid, precipitating tungstic acid, and filtering to obtain crude tungstic acid;
i) Electrodeposition: placing the filtrate obtained in the step b) in a double-membrane three-chamber electrolytic cell, taking copper as a cathode, electrodepositing copper at 40 ℃, and stripping copper on the electrode to obtain recovered copper;
j) Three-effect evaporation: evaporating the electrolyte obtained in the step i) by a three-effect evaporator to obtain distilled water and recycling ammonium sulfate.
Preferably, ammonia water is added in the step a), and a small amount of sodium peroxide and an iron catalyst can be added.
Preferably, the inorganic acid in the step b) is nitric acid, sulfuric acid or hydrochloric acid.
Preferably, the sulfide in the step e) is ammonium sulfide, sodium sulfide or potassium sulfide.
Preferably, the ion exchange column in the step f) is a strongly acidic styrene anion exchange resin column or a weakly acidic styrene anion exchange resin column.
The invention has the beneficial effects that: the invention provides a recovery method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag, which realizes the full recovery of active ingredients in the molybdenum removal slag:
(1) The molybdenum slag is removed through high-temperature high-pressure oxidation and conversion, so that sulfur is converted into sulfate radical, the leaching rate of active ingredients is improved through introducing an oxidant and a catalyst, and the discharge of sulfur oxides is avoided;
(2) A small amount of tungsten in the molybdenum slag is separated by adopting an ion exchange method, so that the discharge of wastewater is reduced;
(3) The recovered copper with higher purity can be obtained by utilizing an electrodeposition method and used for subsequent refining;
(4) The three-effect evaporation recovered ammonium sulfate can be used as an agricultural fertilizer;
the features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
[ description of the drawings ]
FIG. 1 is a process flow diagram of a method for preparing ammonium molybdate and recovering tungsten, copper and sulfur from molybdenum-removed slag according to the present invention;
[ detailed description ] of the invention
The present invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Referring to FIG. 1, a basic composition CuMoS according to the molybdenum removal slag 4 In order to realize the total recovery of molybdenum, tungsten, copper and sulfur components, the invention adopts high temperatureThe high-pressure oxidation reaction is used for carrying out oxidation conversion, and the main chemical reaction equation is as follows in an ammonia medium:
CuMoS 4 +8O 2 +8NH 3 +4H 2 O→(NH 4 ) 2 MoO 4 +CuSO 4 +3(NH 4 ) 2 SO 4
when the reaction is complete, the products have better solubility in water, and a small amount of insoluble residues are filtered and discarded. And then carrying out systematic separation on the solution containing molybdenum, tungsten, copper and sulfur to prepare an ammonium heptamolybdate product, a crude tungstic acid product, a metallic copper product and an ammonium sulfate fertilizer product, so as to realize the full recovery of chemical components of molybdenum removal slag.
Example 1:
500g of the screened molybdenum-removed slag is added into a 2000mL autoclave, 1000mL of 10% ammonia water is added, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the oxygen partial pressure is controlled to be 2.5MPa, the temperature of the autoclave is heated to be 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radical; placing the mixed solution into a 5000mL flask, regulating the pH to 4.0 by using 10% nitric acid for precipitation, and respectively obtaining molybdic acid and tungstic acid mixed precipitation and copper sulfate-containing solution after solid-liquid separation; dissolving the precipitate in 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is regulated to 9.5 under the stirring condition, and a proper amount of FeCl of 2mol/L is added dropwise 3 Dissolving, adding 10% HNO 3 Adjusting the pH value to 6.8, stirring for 4 hours, filtering, and recovering crude tungstic acid from a filter cake; regulating pH of the filtrate to 9.0 with 20% ammonia water, adding small amount of ammonium sulfide, maintaining the temperature for 4 hr, cooling to 40deg.C, and filtering; introducing the filtrate into a weak acid styrene anion exchange resin exchange column, and receiving effluent of the exchange column; the effluent is placed in a 1000mL flask, the pH is regulated to 7.0 by 10% ammonia water under the stirring speed of 150rpm, the temperature is heated to 75 ℃, the effluent is pumped down by a water circulation pump for crystallization, and the ammonium heptamolybdate product is prepared, and can reach molybdic acid by a national standard analysis methodAmmonium national Standard (GB/T3460-2017) MSA-1 and MSA-2 grade product requirements; the recovery rate of molybdenum is calculated to be 93% by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product; desorbing the ion exchange column with 25% ammonia water to obtain a tungstate radical desorption liquid, and regulating the pH value of the tungstate radical desorption liquid to 3.5 with 10% nitric acid to obtain recovered crude tungstic acid; placing the solution containing copper sulfate obtained after acid precipitation into a double-membrane three-chamber electrolytic tank, taking copper as a cathode, electrodepositing copper at 40 ℃, stripping copper on the electrode, and obtaining a recovered copper product; the electrodeposited solution was placed in a 5000mL flask, heated to 70℃of the solution, evacuated to-0.06 MPa with a water circulation vacuum pump, distilled under reduced pressure, and the ammonium sulfate solid was recovered.
Embodiment two:
500g of the screened molybdenum-removed slag is added into a 2000mL autoclave, 1000mL of 10% ammonia water, 5g of sodium peroxide and 5g of ferric nitrate are added, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the partial pressure of the oxygen is controlled to be 2.5MPa, the temperature of the autoclave is heated to be 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radical; placing the mixed solution into a 5000mL flask, regulating the pH to 4.0 by using 10% nitric acid for precipitation, and respectively obtaining molybdic acid and tungstic acid mixed precipitation and copper sulfate-containing solution after solid-liquid separation; dissolving the precipitate in 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is regulated to 9.5 under the stirring condition, and a proper amount of FeCl of 2mol/L is added dropwise 3 Dissolving, adding 10% HNO 3 Adjusting the pH value to 6.8, stirring for 4 hours, filtering, and recovering crude tungstic acid from a filter cake; regulating pH of the filtrate to 9.0 with 20% ammonia water, adding small amount of ammonium sulfide, maintaining the temperature for 4 hr, cooling to 40deg.C, and filtering; introducing the filtrate into a weak acid styrene anion exchange resin exchange column, and receiving effluent of the exchange column; the effluent liquid is placed in a 1000mL flask, the pH is regulated to 7.0 by 10% ammonia water under the stirring speed of 150rpm, the temperature is heated to 75 ℃, the effluent liquid is pumped down by a water circulation pump for crystallization, and the ammonium heptamolybdate product is prepared, and can be obtained by the national standard analysis methodMeets the requirements of ammonium molybdate national standard (GB/T3460-2017) MSA-1 grade and MSA-2 grade products; the recovery rate of molybdenum is calculated to be 98% by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product; desorbing the ion exchange column with 25% ammonia water to obtain a tungstate radical desorption liquid, and regulating the pH value of the tungstate radical desorption liquid to 3.5 with 10% nitric acid to obtain recovered crude tungstic acid; placing the solution containing copper sulfate obtained after acid precipitation into a double-membrane three-chamber electrolytic tank, taking copper as a cathode, electrodepositing copper at 40 ℃, stripping copper on the electrode, and obtaining a recovered copper product; the electrodeposited solution was placed in a 5000mL flask, heated to 70℃of the solution, evacuated to-0.06 MPa with a water circulation vacuum pump, distilled under reduced pressure, and the ammonium sulfate solid was recovered.
Embodiment III:
500g of the screened molybdenum-removed slag is added into a 2000mL autoclave, 1000mL of 10% ammonia water, 5g of sodium peroxide and 5g of ferric nitrate are added, the autoclave is closed, then oxygen is introduced into the autoclave through a pipeline, the partial pressure of the oxygen is controlled to be 2.5MPa, the temperature of the autoclave is heated to be 100 ℃, and the reaction is carried out for 8 hours under stirring. Cooling the autoclave to 40 ℃, taking out the solution, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radical; placing the mixed solution into a 5000mL flask, regulating the pH to 4.0 by using 10% nitric acid for precipitation, and respectively obtaining molybdic acid and tungstic acid mixed precipitation and copper sulfate-containing solution after solid-liquid separation; dissolving the precipitate in 5000mL flask with 10% ammonia water, adjusting pH to 8.5, dissolving all precipitate, and filtering to remove a small amount of insoluble impurities; the pH of the obtained solution is regulated to 9.5 under the stirring condition, and a proper amount of FeCl of 2mol/L is added dropwise 3 Dissolving, adding 10% HNO 3 Adjusting the pH value to 6.8, stirring for 4 hours, filtering, and recovering crude tungstic acid from a filter cake; regulating pH of the filtrate to 9.0 with 20% ammonia water, adding small amount of ammonium sulfide, maintaining the temperature for 4 hr, cooling to 40deg.C, and filtering; introducing the filtrate into a strong acid styrene anion exchange resin exchange column, and receiving effluent of the exchange column; the effluent is placed in a 1000mL flask, the pH is regulated to 7.0 by 10% ammonia water under the stirring speed of 150rpm, the temperature is heated to 75 ℃, the effluent is pumped down by a water circulation pump for crystallization, and the ammonium heptamolybdate product is prepared, and the product is analyzed by national standardThe method can meet the requirements of ammonium molybdate national standard (GB/T3460-2017) MSA-1 grade and MSA-2 grade products; by analyzing the molybdenum content of the raw material and the molybdenum content of the ammonium molybdate product, the recovery rate of molybdenum is calculated to be 95%; desorbing the ion exchange column with 25% ammonia water to obtain a tungstate radical desorption liquid, and regulating the pH value of the tungstate radical desorption liquid to 3.5 with 10% nitric acid to obtain recovered crude tungstic acid; placing the solution containing copper sulfate obtained after acid precipitation into a double-membrane three-chamber electrolytic tank, taking copper as a cathode, electrodepositing copper at 40 ℃, stripping copper on the electrode, and obtaining a recovered copper product; the electrodeposited solution was placed in a 5000mL flask, heated to 70℃of the solution, evacuated to-0.06 MPa with a water circulation vacuum pump, distilled under reduced pressure, and the ammonium sulfate solid was recovered.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (5)
1. A recycling method for preparing ammonium molybdate, tungsten, copper and sulfur by molybdenum removal slag is characterized in that: the method comprises the following steps:
a) High pressure oxygen leaching: crushing, grinding and sieving molybdenum-removing slag, adding 200-300 mesh undersize powder into an autoclave, adding ammonia water at the same time, then introducing oxygen into the autoclave through a pipeline, controlling the oxygen partial pressure to be 2.3-2.7 MPa, heating the autoclave to be at 90-110 ℃, reacting for 8-10 hours under stirring, taking out the solution after the autoclave is cooled to 40 ℃, and filtering to obtain a mixed solution containing molybdenum, tungsten, copper and sulfate radicals and filter residues;
b) Acid precipitation: regulating the pH value of the mixed solution obtained in the step a) to 3.5-4.5 by using 10% inorganic acid, and carrying out solid-liquid separation to obtain a mixed filter cake of molybdic acid and tungstic acid and a filtrate containing copper sulfate respectively;
c) Ammonia dissolution: dissolving the mixed filter cake obtained in the step b) by ammonia water, regulating the pH value to 8.0-8.9,
dissolving the precipitate completely, and filtering to remove a small amount of insoluble impurities to obtain a mixed solution containing molybdate and tungstate;
d) Adsorbing and removing tungsten: regulating the pH value of the mixed solution obtained in the step c) to 9.0-10.0 under the condition of stirring, and dropwise adding 2mol/L FeCl 3 After the addition of the solution, 10% HNO is used 3 Regulating the pH value to 6.5-7.0, stirring for 4 hours, and filtering to obtain filtrate, wherein a filter cake is crude tungstic acid;
e) Purifying: keeping the filtrate obtained in the step d) at 85-90 ℃ and under the condition that the pH value is 8.0-10.0, adding a proper amount of sulfide to precipitate and purify divalent metal in the solution for 3-5 hours, filtering the liquid to obtain filtrate, and discarding a filter cake;
f) Ion exchange: regulating the pH value of the filtrate obtained in the step e) to 7.5-8.5 by using 10% inorganic acid, and then passing the filtrate through an ion exchange column, adsorbing tungstate radicals on the ion exchange column, and flowing out molybdate radicals to obtain a post-exchange liquid;
g) And (3) vacuum crystallization: regulating the pH value of the mixed solution obtained in the step f) to 6.0-7.0, maintaining the temperature of a crystallization kettle at 70-80 ℃, and crystallizing under vacuum condition to obtain ammonium heptamolybdate;
h) Desorbing, precipitating and filtering: desorbing the ion exchange column adsorbing the tungstate radical in the step f) by ammonia water or sodium hydroxide solution to obtain ammonium tungstate or sodium tungstate solution, regulating the pH value of the ammonium tungstate or sodium tungstate solution to 3.0-4.0 by inorganic acid, precipitating tungstic acid, and filtering to obtain crude tungstic acid;
i) Electrodeposition: placing the filtrate obtained in the step b) in a double-membrane three-chamber electrolytic cell, taking copper as a cathode, electrodepositing copper at 40 ℃, and stripping copper on the electrode to obtain recovered copper;
j) Three-effect evaporation: evaporating the electrolyte obtained in the step i) by a three-effect evaporator to obtain distilled water and recycling ammonium sulfate.
2. The recovery method for preparing ammonium molybdate and tungsten, copper and sulfur from molybdenum-removed slag according to claim 1, wherein: and a small amount of sodium peroxide and an iron catalyst are added at the same time of adding ammonia water in the step a).
3. The recovery method for preparing ammonium molybdate and tungsten, copper and sulfur from molybdenum-removed slag according to claim 1, wherein: the inorganic acid in the step b) is nitric acid, sulfuric acid or hydrochloric acid.
4. The recovery method for preparing ammonium molybdate and tungsten, copper and sulfur from molybdenum-removed slag according to claim 1, wherein: the sulfide in the step e) is ammonium sulfide, sodium sulfide or potassium sulfide.
5. The recovery method for preparing ammonium molybdate and tungsten, copper and sulfur from molybdenum-removed slag according to claim 1, wherein: the ion exchange column in the step f) is a strong acid styrene anion exchange resin column or a weak acid styrene anion exchange resin column.
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